Pellicle, Exposure Original Plate with Pellicle, Method for Producing Semiconductor Device, Method for Producing Liquid Crystal Display Board, Method for Regenerating Exposure Original Plate, and Peeling Residue Reduction Method

ABSTRACT

Provided is a pellicle that can reduce residues stuck onto an exposure original plate when the pellicle is peeled from the exposure original plate after being used in lithography, in particular ArF lithography, and also provided are an exposure original plate with a pellicle, a method for regenerating an exposure original plate, and a peeling residue reduction method. 
     A pellicle includes a pellicle film, a pellicle frame provided with the pellicle film on one end face thereof, and an agglutinant layer provided on the other end face of the pellicle frame. When the agglutinant layer of the pellicle is bonded to a quartz mask substrate, then a portion to which the agglutinant layer of the pellicle is bonded is irradiated with 193-nm ultraviolet rays at 10 J/cm 2  from a back surface of the substrate, and the pellicle is peeled after the irradiation, an amount of peeling residues of the agglutinant layer remaining on the substrate is 0.5 mg or less.

FIELD OF THE INVENTION

The present invention relates to a pellicle, an exposure original plate with a pellicle, a method for producing a semiconductor device, a method for producing a liquid crystal display board, a method for regenerating an exposure original plate, and a peeling residue reduction method.

TECHNICAL BACKGROUND OF THE INVENTION

In manufacturing semiconductor devices such as LSI and super-LSI or in manufacturing a liquid crystal display board or the like, a pattern is made by irradiating light to a semiconductor wafer or an original plate for liquid crystal, but if dust is attached to an exposure original plate used in this case, the dust absorbs the light or bends the light. As a result, the transferred pattern would be deformed, and the resulting pattern would have roughened edges or black stains on the base, which would lead to problems such as damaged dimensions, poor quality, and deformed external appearance. In the present invention, the “exposure original plate” is a generic name of lithography masks and reticles.

These works are usually performed in a cleanroom, but it is difficult to keep the exposure original plate clean all the time even in the cleanroom. Therefore, a pellicle that transmits light for exposure well is bonded to a surface of the exposure original plate as a dust-fender.

Under such circumstances, the dust does not directly adhere to the surface of the exposure original plate but adhere only to the pellicle film. Accordingly, when the focus is set on the pattern of the exposure original plate during lithography, the dust on the pellicle film becomes irrelevant to transfer.

The basic structure of the pellicle comprises a pellicle frame and a pellicle film stretched over the pellicle frame. The pellicle film is made of nitrocellulose, cellulose acetate, a fluorine-based polymer, or the like that well transmits light used for exposure (g-rays, i-rays, 248 nm, 193 nm, 157 nm, etc.). The pellicle frame is made of an aluminum alloy such as A7075, A6061, or A5052 treated with black alumite or the like, stainless steel, polyethylene, or the like. A good solvent of a pellicle film is applied to the upper part of the pellicle frame, and the pellicle film is bonded by air-drying or using an adhesive material such as an acrylic resin, an epoxy resin, or fluororesin. Further, since the lower part of the pellicle frame is mounted with an exposure original plate, an agglutinant layer obtained from a polybutene resin, a polyvinyl acetate resin, an acrylic resin, a silicone resin, or the like, and a protective liner for protecting the agglutinant layer are provided.

The pellicle is provided so as to surround a pattern region formed on the surface of the exposure original plate. Since the pellicle is provided to prevent the adhesion of dust to the exposure original plate, the pattern region and the outside of the pellicle are isolated from each other so that dust from the outside of the pellicle does not adhere to the pattern surface.

In recent years, miniaturization of LSI design rules to sub-quarter microns has progressed. Along with this, the wavelength of exposure light sources is becoming shorter. That is, the trend is moving from g-rays (436 nm) and i-rays (365 nm) produced by mercury lamps, which have been the mainstream until now, to KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 laser (157 nm), and the like. As a result of progress in miniaturization, the allowable size of foreign substances and haze that may be generated on the pattern face of the mask substrate to which the pellicle is bonded is becoming more and more strict.

PRIOR ART PUBLICATIONS Publications

-   IP Publication 1: Japanese Patent No. 5638693 -   IP Publication 2: Japanese Patent Application Publication No.     2016-18008 -   IP Publication 3: Japanese Patent Application Publication No.     2006-146085 -   IP Publication 4: Japanese Patent Application Publication No.     2008-21182

SUMMARY OF THE INVENTION Problems the Invention Seeks to Solve

In recent years, phase shift films have been commonly used as mask substrate films to meet the miniaturization of design rules. However, phase shift films are very delicate, and mask cleaning under excessive conditions may cause damage, such as corrosion and scraping, to the phase shift films. For this reason, in recent years, there has been a tendency to reconsider chemicals used for mask cleaning, and to weaken the cleaning conditions.

Furthermore, the mask pattern of advanced mask products is shifting from positive type mask patterns, which have been the mainstream until now, to negative type mask patterns. As a result, there are many situations where no light-shading layer is provided in the portion to which the pellicle is bonded. If there is no light-shading layer, there is a possibility that the pellicle agglutinant is irradiated with an exposure light beam through the mask substrate. In that case, more residues of the agglutinant layer may remain on the mask substrate when the pellicle is peeled.

During use of a pellicle bonded to a mask, if foreign substances and haze are generated, or if the pellicle film is damaged, it is necessary to peel the pellicle, subject the mask to regeneration cleaning, and bond a new pellicle (which is hereinafter referred to as “repellicle”). It is the most important for repellicle that regeneration cleaning is performed so that the mask is kept in a state of high cleanliness; however, in order to carry out regeneration cleaning of the mask under recent weak cleaning conditions, it is important to reduce residues remaining on the mask substrate when the pellicle is peeled.

As regeneration cleaning, cleaning with chemicals such as sulfuric acid hydrogen peroxide or ammonia hydrogen peroxide, and physical cleaning by brushes, sponges, or the like are generally used. However, regeneration cleaning with functional water is being studied to prevent damage to photo masks and sulfate ions from remaining on the photo masks.

Functional water is generally defined by the Japanese Society for Functional Water as, among aqueous solutions that have been given reproducible and useful functions by artificial treatment, those for which the scientific basis for treatment and function has been clarified, and those for which such scientific basis is about to be clarified. Specific examples thereof include fine bubble water such as ozone water, hydrogen water, micro-bubble water, and nano-bubble water; electrolyzed water, supercritical water, subcritical water, and the like. Ozone water and hydrogen water are often used to clean photo masks. In addition, the cleaning power can be improved by adding a small amount of ammonia.

However, the present inventors found that since the cleaning power of functional water was weaker than that of chemicals such as sulfuric acid hydrogen peroxide, in the regeneration cleaning of the photo mask after the removal of the pellicle, residues of the agglutinant layer that fixed the pellicle and the photo mask were difficult to remove only by functional water cleaning. In particular, in phase shift photo masks, damage to phase shift films leads to changes in transmittance and phase difference, and it is thus difficult to add physical cleaning in addition to functional water cleaning.

Moreover, when lithography is performed using an exposure light beam such as ArF excimer laser (193 nm) on a lithography pellicle in which a pellicle film is stretched over the upper end face of a pellicle frame through a pellicle film bonding adhesive material layer, and in which a mask bonding agglutinant layer is provided on the other end face, there is a problem that the agglutinant layer formed on the lower end face of the pellicle frame is altered by the exposure light beam, and many altered parts of the agglutinant layer remain on the exposure original plate as peeling residues when peeling from the exposure original plate.

Attempts have been made so far to reduce residues by adding surface modifiers or the like to agglutinants (IP Publications 1 and 2 described above). Further, as techniques of reducing residues, a large pellicle having an agglutinant layer with a cohesive fracture strength of 20 g/mm² or more (IP Publication 3 described above), and a pellicle comprising an agglutinant for pellicles and having a ratio of peeling strength and tensile strength of 0.10 or more and 0.33 or less are disclosed (IP Publication 4 described above).

The present invention was made in view of such circumstances, and an object of the present invention is to provide a pellicle that can reduce residues stuck onto an exposure original plate when a pellicle is peeled from the exposure original plate after being used in lithography, in particular ArF lithography, and to also provide an exposure original plate with a pellicle, a method for regenerating an exposure original plate, and a peeling residue reduction method. Another object of the present invention is to provide a method for producing a semiconductor device and a method for producing a liquid crystal display board that can thereby improve production efficiency.

Means to Solve the Problems

The above problems of the present invention have been solved by the following means.

[1] A pellicle comprising a pellicle film, a pellicle frame provided with the pellicle film on one end face thereof, and an agglutinant layer provided on the other end face of the pellicle frame, wherein when the agglutinant layer of the pellicle is bonded to a quartz mask substrate, then a portion to which the agglutinant layer of the pellicle is bonded is irradiated with 193-nm ultraviolet rays at 10 J/cm² from a back surface of the substrate, and the pellicle is peeled after the irradiation, an amount of peeling residues of the agglutinant layer remaining on the substrate is 0.5 mg or less.

[2] A pellicle as claimed in [1] described above, wherein the agglutinant that forms the agglutinant layer comprises an acrylic polymer as a base material.

[3] A pellicle as claimed in [2] described above, wherein the acrylic polymer comprises a (meth)acrylic acid ester having an ether bond as a monomer component.

[4] A pellicle as claimed in [3] described above, wherein the (meth)acrylic acid ester having the ether bond is a (meth)acrylic acid ester having an alkylene oxide group.

[5] A pellicle as claimed in [4] described above, wherein the alkylene oxide group is an ethylene oxide group.

[6] A pellicle as claimed in [2] described above, wherein the acrylic polymer has a side chain containing an ether bond.

[7] A pellicle as claimed in [6] described above, wherein the side chain containing the ether bond has an alkylene oxide group.

[8] A pellicle as claimed in [7] described above, wherein the alkylene oxide group is an ethylene oxide group.

[9] A pellicle as claimed in any one of [1] to [8] described above, wherein the agglutinant that forms the agglutinant layer contains a polyvinyl ether compound.

[10] A pellicle as claimed in any one of [1] to [9] described above, wherein the agglutinant layer is irradiated with an exposure light beam.

[11] A pellicle as claimed in any one of [1] to [9] described above, wherein the pellicle is bonded to a phase shift photo mask.

[12] A pellicle as claimed in any one of [1] to [9] described above, wherein the pellicle is bonded to a negative type exposure original plate.

[13] A pellicle as claimed in any one of [1] to [9] described above, wherein the pellicle is bonded to an exposure original plate that has a non-shaded area or a semi-transparent shaded area in a portion thereof to which an agglutinant layer is bonded.

[14] A pellicle as claimed in any one of [1] to [9] described above, wherein the pellicle is bonded to an exposure original plate that has a transparent area in a portion thereof to which an agglutinant layer is bonded.

[15] A pellicle as claimed in any one of [1] to [9] described above, wherein the pellicle is bonded to a face comprising silicon oxide as a main component.

[16] A pellicle as claimed in [15] described above, wherein the face comprising silicon oxide as a main component is a quartz face.

[17] A pellicle as claimed in any one of [1] to [9] described above, wherein the pellicle is compatible with regeneration cleaning with functional water.

[18] An exposure original plate with a pellicle, comprising an exposure original plate and a pellicle as claimed in any one of [1] to [10] described above mounted on the exposure original plate.

[19] An exposure original plate with a pellicle as claimed in [18] described above, wherein the exposure original plate is a phase shift photo mask.

[20] An exposure original plate with a pellicle as claimed in [18] described above, wherein the exposure original plate is of negative type.

[21] An exposure original plate with a pellicle as claimed in [18] described above, wherein a portion of the exposure original plate to which the agglutinant layer is bonded has a non-shaded area or a semi-transparent shaded area.

[22] An exposure original plate with a pellicle as claimed in [18] described above, wherein a portion of the exposure original plate to which the agglutinant layer is bonded has a transparent area.

[23] An exposure original plate with a pellicle as claimed in [18] described above, wherein the exposure original plate comprises silicon oxide as a main component.

[24] An exposure original plate with a pellicle as claimed in [18] described above, wherein the exposure original plate is a quartz substrate.

[25] A method for producing a semiconductor device, comprising a step of performing exposure using an exposure original plate with a pellicle as claimed in any one of [18] to [24] described above.

[26] A method for producing a liquid crystal display board, comprising a step of performing exposure using an exposure original plate with a pellicle as claimed in any one of [18] to [24] described above.

[27] A method for regenerating an exposure original plate, comprising peeling a pellicle from an exposure original plate with a pellicle as claimed in any one of [18] to [24] described above, and cleaning residues of an agglutinant remaining on the exposure original plate with functional water to regenerate the exposure original plate.

[28] A peeling residue reduction method comprising, when peeling a pellicle from an exposure original plate to which the pellicle is bonded, reducing peeling residues of an agglutinant layer of the pellicle remaining on the exposure original plate, wherein the method uses a pellicle as claimed in any one of [1] to [17] described above as the pellicle.

[29] An application of a pellicle comprising a pellicle film, a pellicle frame provided with the pellicle film on one end face thereof, and an agglutinant layer provided on the other end face of the pellicle frame, wherein the agglutinant layer is irradiated with an exposure light beam.

[30] An application of a pellicle comprising a pellicle film, a pellicle frame provided with the pellicle film on one end face thereof, and an agglutinant layer provided on the other end face of the pellicle frame, wherein the pellicle is bonded to a phase shift photo mask.

[31] An application of a pellicle comprising a pellicle film, a pellicle frame provided with the pellicle film on one end face thereof, and an agglutinant layer provided on the other end face of the pellicle frame, wherein the pellicle is bonded to a negative type exposure original plate.

[32] An application of a pellicle comprising a pellicle film, a pellicle frame provided with the pellicle film on one end face thereof, and an agglutinant layer provided on the other end face of the pellicle frame, wherein the pellicle is bonded to an exposure original plate that has a non-shaded area or a semi-transparent shaded area in a portion thereof to which the agglutinant layer is bonded.

[33] An application of a pellicle comprising a pellicle film, a pellicle frame provided with the pellicle film on one end face thereof, and an agglutinant layer provided on the other end face of the pellicle frame, wherein the pellicle is bonded to an exposure original plate that has a transparent area in a portion thereof to which the agglutinant layer is bonded.

[34] An application of a pellicle comprising a pellicle film, a pellicle frame provided with the pellicle film on one end face thereof, and an agglutinant layer provided on the other end face of the pellicle frame, wherein the pellicle is bonded to a face comprising silicon oxide as a main component (in particular, a quartz face).

[35] An application of a pellicle comprising a pellicle film, a pellicle frame provided with the pellicle film on one end face thereof, and an agglutinant layer provided on the other end face of the pellicle frame, wherein the pellicle is compatible with regeneration cleaning with functional water.

[36] A peeling residue reduction pellicle comprising at least a pellicle film, a pellicle frame having one end face to which the pellicle film is bonded, and an agglutinant layer for bonding the pellicle to an exposure original plate provided on the other end face of the pellicle frame, wherein when the agglutinant layer of the pellicle is bonded to a quartz mask substrate, then a portion to which the agglutinant layer of the pellicle is bonded is irradiated with 193-nm ultraviolet rays at 10 J/cm² from a back surface of the substrate, and the pellicle is peeled after the irradiation, an amount of peeling residues of the agglutinant layer remaining on the substrate is 0.5 mg or less.

[37] A peeling residue reduction pellicle as claimed in [36] described above, wherein the agglutinant layer comprises an agglutinant containing an acrylic polymer.

[38] A peeling residue reduction pellicle as claimed in [37] described above, wherein 51 mass % or more of all the monomer components that constitute the acrylic polymer is an ethylene oxide group-containing (meth)acrylate monomer.

[39] A peeling residue reduction pellicle as claimed in [37] or [38] described above, wherein the agglutinant further contains a polyvinyl ether compound.

[40] A peeling residue reduction pellicle as claimed in any one of [36] to [39] described above, wherein the peeling residue reduction pellicle is a peeling residue reduction pellicle for ArF lithography.

[41] A method for reducing, when a pellicle is peeled from an exposure original plate to which the pellicle is bonded, peeling residues of an agglutinant layer of the pellicle remaining on the exposure original plate, wherein the method uses a pellicle as claimed in any one of [36] to [40] described above as the pellicle.

[42] A method for selecting a peeling residue reduction pellicle, the method comprising:

a step of bonding an agglutinant layer of a pellicle, which is a selection candidate, to a quartz photo mask substrate;

a step of irradiating a portion to which the agglutinant layer of the pellicle is bonded with 193-nm ultraviolet rays at 10 J/cm² from a back surface of the substrate; and

a step of selecting, as the peeling residue reduction pellicle, a pellicle in which when peeling the pellicle after the irradiation, an amount of peeling residues of the agglutinant layer remaining on the substrate is 0.5 mg or less.

Effects of the Invention

The present invention can provide a pellicle that can reduce peeling residues stuck onto an exposure original plate when a pellicle is peeled from the exposure original plate after being used in lithography, in particular ArF lithography, and can also provide an exposure original plate with a pellicle, a method for regenerating an exposure original plate, and a peeling residue reduction method. According to the pellicle, exposure original plate with a pellicle, method for regenerating an exposure original plate, and peeling residue reduction method of the present invention, even when an exposure light beam is applied through the exposure original plate, the pellicle can be peeled from the exposure original plate with very few peeling residues of the agglutinant. As a result, the regeneration cleaning of the exposure original plate, from which the pellicle is removed, can proceed smoothly, and the cleaning conditions can be loosened; thus, there is an advantage in reducing damage to the exposure original plate surface during cleaning. In addition, production efficiency can be improved in the production of semiconductor devices and liquid crystal display boards.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 A conceptual diagram showing the basic structure of the pellicle of the present invention.

EXAMPLES TO EMBODY THE INVENTION

First, the basic structure of the pellicle of the present invention will be described with reference to FIG. 1.

As shown in FIG. 1, the pellicle 10 of the present invention is such that a pellicle film 12 is stretched over the upper end face of a pellicle frame 11 through an adhesive material layer 13 for bonding the pellicle film. In this case, an agglutinant layer 14 for bonding the pellicle 10 to an exposure original plate (mask substrate or reticle) 1 is generally formed on the lower end face of the pellicle frame 11, and a liner (not shown) is peelably bonded to the lower end face of the agglutinant layer 14. In addition, the pellicle frame 11 may be provided with an air pressure adjustment hole (vent) 15, and may be further provided with a dust removal filter 16 for the purpose of removing particles.

In this case, the size of these pellicle constituent members is equivalent to that of general pellicles, for example, pellicles for semiconductor lithography and pellicles for the lithography step in the production of large liquid crystal display boards. Moreover, the materials thereof can be known materials as described above.

The type of pellicle film 12 is not particularly limited. For example, amorphous fluoropolymers conventionally used for excimer laser are used. Examples of amorphous fluoropolymers include Cytop (trade name of AGC Inc.), Teflon (registered trademark) AF (trade name of DuPont), and the like. These polymers may be used after being dissolved in solvents, if necessary, during the production of pellicle films, and can be suitably dissolved, for example, in fluorine type solvents.

As for the base material of the pellicle frame 11, for example, aluminum alloy materials, preferably JIS A7075, JIS A6061, and JIS A5052 materials, are used. When an aluminum alloy material is used, there is no particular limitation as long as the strength as the pellicle frame is ensured. The pellicle frame surface is preferably roughened by sandblasting or chemical polishing, and a polymer coating may be provided after roughening. In the present invention, a conventionally known method can be employed as the method for roughening the frame surface. In a preferable method, the surface of an aluminum alloy material is subjected to blast treatment using stainless steel, carborundum, glass beads, or the like, and is further subjected to chemical polishing using NaOH or the like, thereby roughening the surface.

The agglutinant used to form the agglutinant layer 14 can be suitably selected from various agglutinants, described later; however, acrylic agglutinants are preferable. Further, in order to reduce distortion and other influences on the mask substrate to which the pellicle is bonded, and to suppress residual stress due to pellicle bonding, the shape of such agglutinants is preferably a flat shape that is less likely to deform during bonding of the pellicle.

In the pellicle of the present invention, the thickness of the agglutinant layer 14 is generally preferably 150 to 500 μm, more preferably 180 to 350 μm, and particularly preferably 200 to 300 μm. Further, the width of the agglutinant layer 14 may be suitably determined depending on the width of the pellicle frame 11. In general, the agglutinant layer is provided over the entire circumference of the lower end face of the pellicle frame 11 in the circumferential direction with the same width as the width of the pellicle frame.

The pellicle of the present invention is a peeling residue reduction pellicle characterized in that when the agglutinant layer of the pellicle is bonded to a quartz mask substrate, then a portion to which the agglutinant layer of the pellicle is bonded is irradiated with 193-nm ultraviolet rays at 10 J/cm² from the back surface of the substrate, and the pellicle is peeled after the irradiation, an amount of peeling residues of the agglutinant layer remaining on the substrate is 0.5 mg or less. Here, the peeling residue reduction pellicle refers to a lithography pellicle in which, when the pellicle is peeled from an exposure original plate after being used in lithography, peeling residues of the agglutinant layer remaining on the surface of the exposure original plate can be reduced, that is, a lithography pellicle in which peeling residues are less likely to be generated.

When the agglutinant layer of the pellicle is bonded to a quartz mask substrate, examples of the quartz mask substrate include a substrate of a quartz mask 6025 size (152 mm×152 mm, t=6.35 mm). Therefore, the pellicle of the present invention basically has a size that can be bonded to the quartz mask 6025 size. Specifically, the external form is generally within the range of 150 to 145 mm×124 to 100 mm. Further, the width of the pellicle frame that constitutes the pellicle of the present invention is generally in the range of 1.7 to 2.1 mm, and preferably 1.8 to 2.0 mm, and the thickness of the pellicle frame is generally in the range of 2.0 to 6.2 mm, and preferably 2.5 to 6.0 mm.

When the agglutinant layer of the pellicle is bonded to a quartz mask substrate, bonding is performed at a bonding load of 10 to 250 N, and preferably 40 to 100 N, for a load time of 15 to 120 seconds, and preferably 20 to 60 seconds. After the agglutinant layer of the pellicle is bonded to the quartz mask substrate, the resultant is left at room temperature (20±3° C.) for 12 to 24 hours, and then irradiated with ultraviolet rays with the above wave length at 10 J/cm² from the back surface of the mask substrate so that the ultraviolet rays are applied to the portion to which the agglutinant layer is bonded.

In the present invention, the reason why the irradiation amount is 10 J/cm² is that it is supposed that 1% of the irradiation amount of 1000 J on the mask (about 10000 J in conversion on the wafer) is applied to the mask agglutinant as stray light.

When the pellicle is peeled after the irradiation, a side of the pellicle is held using a peeling device or the like at room temperature, and pulled upward (90° direction) to the mask surface at a speed of 0.1 mm/sec to completely peel the pellicle from the mask substrate. After peeling, the mass difference of the mask substrate before and after peeling is measured. A pellicle in which this mass difference (amount of peeling residues) is 0.5 mg or less, and preferably 0.2 mg or less, is the pellicle of the present invention. Since the amount of peeling residues is small, re-cleaning of the exposure original plate becomes extremely easy.

It is preferable that two holes with a hole center spacing of 104 mm are provided on the outer surface of the long side of the pellicle frame. The pellicle frame has two long sides, each of which is preferably provided with two holes. The two holes are preferably provided so that the distance from one end of the long side to one hole and the distance from the other end of the long side to the other hole are the same. In terms of the device, each hole is preferably about 1.6 mm in diameter and 1.0 mm or more and less than 1.8 mm in depth. The pellicle can be easily peeled by inserting four pins of the peeling device into these four holes and pulling them up. The pulling speed can be changed in the range of 0.1 mm/sec or less depending on the peeling strength. Further, when pulling up, instead of pulling up two long sides at the same time, pulling up from one long side can reduce the peeling force applied to the left and right.

As described above, in the agglutinant layer of the present invention, the amount of peeling residues remaining on the substrate is equal to or less than a predetermined amount. This can be achieved, for example, according to the design guidelines listed in the following (1) to (5).

(1) The hydrophilicity of the agglutinant is increased. (2) When the base material contained in the agglutinant is an acrylic copolymer, an ether bond is introduced into the side chain thereof. (3) When the base material contained in the agglutinant is a chain-like polymer, the degradability of the side chain thereof by irradiation with an exposure light beam is set higher than the degradability of the main chain. (4) When the base material contained in the agglutinant is a chain-like polymer, the side chain thereof is selectively deteriorated by irradiation with an exposure light beam. (5) The cohesive force of the entire agglutinant is increased.

In (1) above, the hydrophilicity can be controlled using an SP value (solubility parameter). For example, when an acrylic polymer is used as the base material of the agglutinant, the SP value is preferably controlled to about 10.0 or more and 12.0 or less. The SP value can be determined by the following Equation 1 with reference to the Fedors calculation method [“Polymer Engineering and Science,” Vol. 14, No. 2 (1974), pp. 148-154].

$\begin{matrix} {\delta = \left( \frac{\sum\limits_{i}{\Delta ei}}{\sum\limits_{i}{\Delta\;{vi}}} \right\rbrack^{\frac{1}{2}}} & \left\lbrack {{Equation}\mspace{14mu} 1} \right\rbrack \end{matrix}$

In the above Equation 1, δ is a solubility parameter (SP value), Δei is molar evaporation energy, and Δvi is molar volume. Further, the unit of the solubility parameter is (cal/mol)^(1/2). Table 1 shows the eigenvalues of Δei and Δvi given to the main atoms or atomic groups with respect to the above Equation 1.

TABLE 1 Atom or atomic group

 ei (cal/mol)

 vi (cm³/mol) C 350 −19.2 —CH₂— 1180 16.1 —CH₃ 1125 33.5 CH₂═ 1030 28.5 —CH═ 1030 13.5 -phenyl 7630 71.4 —O— 800 3.8 —CO— 4150 10.8 —COO— 4300 18.0 —OH 7120 10.0 —CONH₂ 10000 17.5 —CONH— 8000 9.5 —NH₂ 3000 19.2 —NH— 2000 4.5 —CN 6100 24.0 —COOH 6600 28.5 Si 810 0.0 F 1000 18.0 Cl 2760 24.0

The SP value (solubility parameter) of the acrylic polymer is preferably 10.0 to 12.0, and more preferably 10.0 to 11.0.

The SP value of the acrylic polymer can be controlled, for example, by changing the concentration of polar groups in the acrylic polymer. For example, when a relatively higher polar bond, such as an ether bond, is introduced into the side chain, the SP value tends to increase. On the other hand, when a relatively less polar bond, such as a long-chain alkylene bond, is introduced into the side chain, the SP value tends to decrease.

In (2) above, the ether bond to be introduced into the side chain is preferably an alkylene oxide group, and particularly preferably an ethylene oxide group. Due to the introduction of an ether bond into the side chain, the ether bond is assumed to prevent light-deterioration of the main chain.

In (3) above, the difference in degradability can be determined, for example, by comparing the decomposition product of the main chain and the decomposition product of the side chain before and after irradiation of the agglutinant with an exposure light beam by IR, NMR, or the like. More specifically, it can be confirmed by comparing the IR chart of the agglutinant before irradiation with an exposure light beam with the IR chart of the agglutinant after irradiation with an exposure light beam, and observing the change in spectral intensity. Examples of the wave number to be confirmed include C—O—C(methoxy group) at 1125 cm⁻¹, C—O—C(ether group) at 1160 cm⁻¹, C═O (ester group) at 1727 cm⁻¹, and the like.

In (4) above, the presence of deterioration can be determined, for example, by comparing the decomposition product of the main chain and the decomposition product of the side chain before and after irradiation of the agglutinant with an exposure light beam by IR, NMR, or the like. More specifically, it can be confirmed by comparing the IR chart of the agglutinant before irradiation with an exposure light beam with the IR chart of the agglutinant after irradiation with an exposure light beam, and observing the change in spectral intensity. Examples of the wave number to be confirmed include C—O—C(methoxy group) at 1125 cm⁻¹, C—O—C(ether group) at 1160 cm⁻¹, C═O (ester group) at 1727 cm⁻¹, and the like.

In (5) above, the cohesive force of the agglutinant can be controlled, for example, by adjusting the crosslinking density of a polymer, a resin, or the like that is used as the base material, or by incorporating a compound having different physical properties, such as a polyvinyl ether compound, in addition to the base material of the agglutinant.

Examples of the agglutinant used to form the agglutinant layer 14 include agglutinants containing an acrylic polymer, a silicone resin, a thermoplastic elastomer, or the like. Since various monomer components can be selected for acrylic polymers, design suitable for the required agglutinant characteristics can be easily made. Silicone resins have excellent balance between light resistance, adhesion characteristics, peeling characteristics, etc. Thermoplastic elastomers are highly cost competitive. Acrylic agglutinants are preferable.

The acrylic polymer mentioned above is, for example, a polymer comprising a (meth)acrylic acid ester as a monomer component, and a monomer component copolymerizable with the (meth)acrylic acid ester can be copolymerized, if necessary. Examples of the (meth)acrylic acid ester include (meth)acrylic acid esters having an ether bond, (meth)acrylic acid alkyl esters, unsaturated monomers having a carboxyl group or a hydroxyl group, and the like. When a (meth)acrylic acid ester having an ether bond is contained as a monomer component, the ether bond can be introduced into the side chain of the acrylic polymer.

Examples of the (meth)acrylic acid ester having an ether bond ((A) component) include (meth)acrylic acid esters having an alkylene oxide group, such as an ethylene oxide group, a propylene oxide group, or a butylene oxide group. Among these, (meth)acrylic acid esters having an ethylene oxide group (also referred to as ethylene oxide group-containing (meth)acrylates) are preferable. Examples thereof include methoxypolyethylene glycol (meth)acrylates, such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, phenoxyethylene glycol (meth)acrylate, and methoxydiethylene glycol (meth)acrylate; ethoxypolyethylene glycol (meth)acrylates, such as ethoxydiethylene glycol (meth)acrylate; butoxypolyethylene glycol (meth)acrylates, such as butoxydiethylene glycol (meth)acrylate; phenoxypolyethylene glycol (meth)acrylates, such as phenoxydiethylene glycol (meth)acrylate; and the like. These may be used singly or in combination of two or more.

Examples of the (meth)acrylic acid alkyl ester ((B) component) include (meth)acrylic acid alkyl esters having a C₁₋₁₄ alkyl group, and the like. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, and the like. Among these, (meth)acrylic acid alkyl esters having a C₄ or C₈ alkyl group are preferable, in terms of satisfying both agglutinant characteristics and peeling characteristics. These may be used singly or in combination of two or more.

Examples of the unsaturated monomer having a carboxyl group or a hydroxyl group ((C) component) include α,β-unsaturated carboxylic acids, such as (meth)acrylic acid, maleic acid, crotonic acid, itaconic acid, and fumaric acid; hydroxyl group-containing methacrylates, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate; and the like. These may be used singly or in combination of two or more.

The ratio of the (A) component used in the acrylic polymer is preferably 30 mass % or more, more preferably 35 mass % or more, particularly preferably 35 to 98 mass %, and extremely preferably 40 to 95 mass %, in the whole monomer components. Because of the ratio of the (A) component within the above range, it becomes easy to control peeling residues and light resistance.

The ratio of the (B) component used in the acrylic polymer is preferably 0 to 70 mass %, and more preferably 3 to 55 mass %, in the whole monomer components. Because of the ratio of the (B) component within the above range, it becomes easy to control adhesion.

The ratio of the (C) component used in the acrylic polymer is preferably 0 to 10 mass %, and more preferably 2 to 8 mass % in the whole monomer components. Because of the ratio of the (C) component within the above range, it becomes easy to control peeling residues and the degree of crosslinking due to the reaction with a curing agent.

The acrylic polymer can be produced, for example, by selecting a known production method, such as solution polymerization, bulk polymerization, emulsion polymerization, or radical polymerization. Further, the obtained acrylic polymer may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.

When the molecular weight of the acrylic polymer is within the range of 700,000 to 2.5 million as weight average molecular weight, the agglutinant layer has moderate cohesive force and adhesive strength, and the agglutinant causes less adhesive residues and has sufficient adhesive strength and load resistance, which is preferable.

The weight average molecular weight mentioned above is a value measured by gel permeation chromatography (GPC) analysis, and refers to a value in terms of standard polystyrene. The GPC analysis can be performed using tetrahydrofuran (THF) as an eluent.

In the present embodiment, a reaction product of the acrylic polymer and a curing agent is preferably contained as the agglutinant of the agglutinant layer; however, in terms of flexibility, an acrylic polymer that does not react with the curing agent may be contained.

The curing agent is not particularly limited as long as it is a curing agent that is used as a general agglutinant, and examples thereof include metal salts, metal alkoxides, aldehyde type compounds, non-amino resin type amino compounds, urea type compounds, isocyanate type compounds, polyfunctional epoxy compounds, metal chelate type compounds, melamine type compounds, aziridine type compounds, and the like. Among these, isocyanate type compounds and epoxy compounds are preferable, in terms of the reactivity with the carboxyl group or the hydroxyl group.

Examples of isocyanate type compounds include xylylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, and multimers, derivatives, and polymers thereof, and the like. These may be used singly or in combination of two or more.

Examples of epoxy compounds include compounds having two or more epoxy groups in the molecule, and specific examples thereof include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diamine glycidylamine, N,N,N′,N′-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N′-diamineglycidylaminomethyl), and the like. These may be used singly or in combination of two or more.

As the silicone resin, for example, silicone resins known as agglutinants can be suitably used. Specific examples thereof include those obtained by partial dehydration condensation of an organopolysiloxane having silanol groups at both ends of the molecular chain, with an organopolysiloxane having a triorganosiloxane unit represented by R₃SiO_(0.5) (wherein R is a substituted or unsubstituted monovalent hydrocarbon group) and an Sift unit in the molecule, and the like. These are available as silicone type agglutinants KR-101-10, KR-120, KR-130, and X-40-3068 (all are trade names of Shin-Etsu Chemical Co., Ltd.).

Examples of the thermoplastic elastomer include styrene type thermoplastic elastomers, (meth)acrylic acid ester type thermoplastic elastomers, olefin type thermoplastic elastomers, and the like. More specifically, the thermoplastic elastomer described in Japanese Patent No. 5513616 can be used.

Among these high-molecular-weight components, acrylic polymers are preferable because the mixability with the polyvinyl ether compound can be easily controlled. These high-molecular-weight components may be used singly or in combination of two or more.

In the present invention, the “agglutinant comprising an acrylic polymer as a base material” refers to an agglutinant containing an acrylic polymer itself or an agglutinant containing a reaction product of the acrylic polymer, a curing agent, and the like.

The content of the acrylic polymer in the entire mass of the agglutinant that forms the agglutinant layer 14 is generally 90 to 99 mass %, preferably 92 to 98 mass %, and particularly preferably 94 to 96 mass %, in terms of reducing peeling residues.

The agglutinant that forms the agglutinant layer 14 preferably further contains a polyvinyl ether compound in addition to the base material, such as an acrylic polymer mentioned above. The combined use of a polyvinyl ether compound, which is used as the agglutinant, is further effective for reducing the amount of peeling residues. Examples of the polyvinyl ether compound include homopolymers of vinyl ethers, such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, and (2-methoxyethyl) vinyl ether; copolymers of two or more vinyl ethers; copolymers of these vinyl ethers and other monomers; and the like. Among these, polyvinyl ether compounds containing methyl vinyl ether as a raw material monomer component are preferable in terms of the control of peeling residues.

In the agglutinant that forms the agglutinant layer 14, the mixing ratio of the base material, such as an acrylic polymer mentioned above, and the polyvinyl ether compound is, based on mass, 90:10 to 99:1, preferably 92:8 to 98:2, and particularly preferably 94:6 to 96:4, in terms of reducing peeling residues.

In addition, the agglutinant that forms the agglutinant layer of the pellicle may be mixed with other components, such as crosslinking agents, tackifiers, plasticizers, stabilizers, viscosity regulators, antistatic agents, lubricants, conductivity-imparting agents, flame retardancy-imparting agents, thermal conductivity-improving agents, heat resistance-improving agents, weather resistance-improving agents, thixotropy-imparting agents, antioxidants, antimicrobial agents, antifungal agents, and coloring agents, depending on the purpose within the range in which the characteristics of the present invention are not impaired.

As the means for forming the agglutinant layer 14, an uncured liquid or paste agglutinant is applied to the lower end face of the pellicle frame 11, followed by curing treatment, thereby forming an agglutinant layer. The agglutinant may be applied once, or may be repeatedly applied several times in order to obtain a predetermined thickness of the agglutinant layer. In this case, the agglutinant is preferably allowed to stand between each time of coating until the shape of the agglutinant after coating is stabilized. If it is difficult to apply an agglutinant due to its high viscosity, the agglutinant may be applied, if necessary, after dilution with an organic solvent, alcohol, water, or the like to reduce the viscosity of the agglutinant. The agglutinant can be applied, for example, by dipping, spraying, or brush coating, or by using a coating device with a dispenser or the like. Coating using a coating device with a dispenser is preferable, in terms of stability, workability, yield, and the like.

In the production of the pellicle 10, the coating and formation of the agglutinant layer 14 are generally performed first, followed by stretching of the pellicle film 12; however, the order may be reversed. For stretching the pellicle film 12, for example, an adhesive material is applied to the upper end face of the pellicle frame 11, and the pellicle frame 11 is then heated to cure the adhesive material. Finally, the upper end face of the pellicle frame 11, on which the adhesive material layer 13 for bonding a pellicle film is formed, is bonded to a pellicle film taken in an aluminum frame larger than the pellicle frame 11, and extra portions of the pellicle film protruding outside the pellicle frame 11 are removed, thereby completing the pellicle.

Due to the use of the pellicle of the present invention with the configuration described above, the amount of agglutinant residues can be reduced when the pellicle is peeled from the exposure original plate after being used in lithography. Moreover, the present invention provides a method for reducing peeling residues of the agglutinant layer of the pellicle by using the pellicle of the present invention. Therefore, the pellicle of the present invention is useful as a pellicle bonded to a phase shift photo mask having the delicate phase shift film mentioned above, or a face comprising silicon oxide, such as quartz, as a main component.

The pellicle of the present invention is also useful as a pellicle applied to exposure original plates whose agglutinant layer is irradiated with an exposure light beam during exposure, such as a negative type exposure original plate, an exposure original plate that has a non-shaded area or a semi-transparent shaded area in a portion thereof to which an agglutinant is bonded, and an exposure original plate that has a transparent area in a portion thereof to which an agglutinant is bonded. The agglutinant layer of the pellicle used in such an exposure original plate is exposed to an exposure light beam through the exposure original plate from the face of the exposure original plate opposite to the face provided with the pellicle.

The pellicle of the present invention may be used not only as a protective member for suppressing the adhesion of foreign substances to the exposure original plate in the exposure device, but also as a protective member for protecting the exposure original plate during storage or transportation of the exposure original plate. An exposure original plate with a pellicle can be produced by mounting the pellicle described above on an exposure original plate, such as a photo mask.

The method for producing a semiconductor device or a liquid crystal display board according to the present embodiment comprises a step of exposing a substrate (semiconductor wafer or liquid crystal original plate) using the exposure original plate with a pellicle described above. For example, in the lithography step, which is one of the steps for producing semiconductor devices or liquid crystal display boards, in order to form a photoresist pattern corresponding to an integrated circuit etc. on a substrate, the exposure original plate with a pellicle described above is set on a stepper to perform exposure. As a result, if foreign substances adhere to the pellicle in the lithography step, the foreign substances do not form images on the wafer coated with a photoresist; thus, the short circuit, disconnection, and the like of the integrated circuit etc. due to images of the foreign substances can be prevented. Therefore, the use of the exposure original plate with a pellicle can improve the yield in the lithography step.

In general, when a desired number of times of lithography steps are performed, when foreign substances and haze are generated, or when the pellicle film is damaged, the pellicle is peeled from the exposure original plate, and the exposure original plate is subjected to regeneration cleaning in some cases. Due to the use of the pellicle of the present invention, peeling residues during repellicle can be reduced even in the case of exposure original plates whose agglutinant layer is irradiated with an exposure light beam during exposure, such as an exposure original plate having a face comprising silicon oxide as a main component in which peeling residues of the agglutinant layer are likely to be generated, a negative type exposure original plate whose agglutinant layer is irradiated with an exposure light beam more than before, an exposure original plate that has a non-shaded area or a semi-transparent shaded area in a portion thereof to which an agglutinant is bonded, whose agglutinant layer is irradiated with an exposure light beam more than before, and an exposure original plate that has a transparent area in a portion thereof to which an agglutinant is bonded, whose agglutinant layer is irradiated with an exposure light beam more than before.

Moreover, since the use of the pellicle of the present invention can reduce peeling residues of the agglutinant layer, cleaning with functional water can be easily applied, and cleaning properties for delicate exposure original plates, such as phase shift photo masks, can be improved. In addition, the use of the pellicle of the present invention can contribute to the reduction of environmental burden caused by cleaning with functional water.

EXAMPLES

The present invention will be described in more detail below with reference to Examples. The “mask” in the Examples and Comparative Examples is described as an example of the “exposure original plate.” Needless to say, it can also be applied to reticles.

Example 1

After a pellicle frame (external size: 149 mm×115 mm×3 mm, thickness: 2 mm, flatness of an end face coated with a mask bonding agglutinant: 15 um) made of an aluminum alloy was subjected to precision cleaning, an acrylic agglutinant manufactured by Soken Chemical Co., Ltd. (product name: SK-Dyne SN-70A, containing, as a base material, an acrylic polymer in which 95 mass % of monomer components was an ethylene oxide group-containing (meth)acrylate, and 2 mass % (solid content) of a polyvinyl ether compound based on 30 mass % (solid content) of the acrylic polymer) was applied to the end face with a flatness of 15 um over the entire circumference of the end face in the circumferential direction with the same width as the width of the pellicle frame, and allowed to stand for 60 minutes at room temperature. Thereafter, a separator was placed on an aluminum plate with a flatness of 5 um, and the pellicle frame coated with the agglutinant was placed so that the agglutinant faced down. Thus, the agglutinant was brought into contact with the flat separator and flattened.

Next, the pellicle on the aluminum plate was placed in an oven at 60° C. for 60 minutes to cure the agglutinant, thereby forming an agglutinant layer with a thickness of 240 um.

After the pellicle together with the aluminum plate was taken out from the oven, the separator was peeled.

Thereafter, an adhesive material manufactured by AGC Inc. (trade name: Cytop CTX-A) was applied to the end face opposite to the end face coated with the agglutinant. Then, the pellicle frame was heated at 130° C. to cure the adhesive material.

Finally, the adhesive material-coated end face of the pellicle frame was bonded to a pellicle film taken in an aluminum flame larger than the pellicle frame, and portions outside the pellicle frame were removed, thereby completing the pellicle.

Next, the mass of a 6025 mask substrate was measured and recorded. The mask substrate whose mass was measured and the previously prepared pellicle were set in a bonding device, and pressurized at a bonding load of 50 N for a load time of 30 seconds to bond the pellicle to the mask substrate.

After the mask substrate to which the pellicle was bonded was left for 24 hours at room temperature, the back surface of the mask was irradiated with ultraviolet rays at 10 mJ/cm² using a 193-nm ultraviolet lamp so that the light beam was applied to the pellicle agglutinant.

After ultraviolet irradiation, the resultant was left for 1 hour at room temperature, and then the pellicle was slowly peeled upward from the mask substrate at a speed of 0.1 mm/sec.

When the mask substrate after peeling was visually observed, a slightly pale band was found in the contour portion to which the pellicle was bonded. The mass of the substrate after peeling was measured, and compared with the measured value before bonding. As a result, the mass difference was +0.08 mg.

Example 2

A pellicle was completed in the same manner using the same materials as in Example 1, except that the mask bonding agglutinant used herein was an acrylic agglutinant manufactured by Soken Chemical Co., Ltd. (product name: SN-25B, containing, as a base material, an acrylic polymer in which 40 mass % of monomer components was an ethylene oxide group-containing (meth)acrylate). The resulting pellicle was bonded to a 6025 mask substrate, as in Example 1.

After the mask substrate to which the pellicle was bonded was left for 24 hours at room temperature, the back surface of the mask was irradiated with ultraviolet rays at 10 J/cm² using a 193-nm ultraviolet lamp so that the light beam was applied to the pellicle agglutinant, as in Example 1.

After ultraviolet irradiation, the resultant was left for 1 hour at room temperature, and then the pellicle was slowly peeled upward from the mask substrate at a speed of 0.1 mm/sec.

When the mask substrate after peeling was visually observed, a slightly pale band was found in the contour portion to which the pellicle was bonded. The mass of the substrate after peeling was measured, and compared with the measured value before bonding. As a result, the mass difference was +0.09 mg.

Example 3

A pellicle was completed in the same manner using the same materials as in Example 1, except that the mask bonding agglutinant used herein was an acrylic agglutinant manufactured by Soken Chemical Co., Ltd. (product name: SN-24C, containing, as a base material, an acrylic polymer in which 90 mass % of monomer components was an ethylene oxide group-containing (meth)acrylate). The resulting pellicle was bonded to a 6025 mask substrate, as in Example 1.

After the mask substrate to which the pellicle was bonded was left for 24 hours at room temperature, the back surface of the mask was irradiated with ultraviolet rays at 10 J/cm² using a 193-nm ultraviolet lamp so that the light beam was applied to the pellicle agglutinant, as in Example 1.

After ultraviolet irradiation, the resultant was left for 1 hour at room temperature, and then the pellicle was slowly peeled upward from the mask substrate at a speed of 0.1 mm/sec.

When the mask substrate after peeling was visually observed, a slightly pale band was found in the contour portion to which the pellicle was bonded. The mass of the substrate after peeling was measured, and compared with the measured value before bonding. As a result, the mass difference was +0.08 mg.

Comparative Example 1

A pellicle was completed in the same manner using the same materials as in Example 1, except that the mask bonding agglutinant used herein was an acrylic agglutinant manufactured by Soken Chemical Co., Ltd. (product name: SK-Dyne SK-1425S, ethylene oxide group-containing (meth)acrylate monomer: 0 mass %, other (meth)acrylate monomers: 100 mass %). The resulting pellicle was bonded to a 6025 mask substrate, as in Example 1.

After the mask substrate to which the pellicle was bonded was left for 24 hours at room temperature, the back surface of the mask was irradiated with ultraviolet rays at 10 J/cm² using a 193-nm ultraviolet lamp so that the light beam was applied to the pellicle agglutinant, as in Example 1.

After ultraviolet irradiation, the resultant was left for 1 hour at room temperature, and then the pellicle was slowly peeled upward from the mask substrate at a speed of 0.1 mm/sec.

When the mask substrate after peeling was visually observed, pale agglutinant residues were found in the portion to which the pellicle was bonded. The mass of the substrate after peeling was measured, and compared with the measured value before bonding. As a result, the mass difference was +0.58 mg.

Comparative Example 2

A pellicle was completed in the same manner using the same materials as in Example 1, except that the mask bonding agglutinant used herein was a silicone agglutinant manufactured by Shin-Etsu Chemical Co., Ltd. (product name: X40-3122). The resulting pellicle was bonded to a 6025 mask substrate, as in Example 1.

After the mask substrate to which the pellicle was bonded was left for 24 hours at room temperature, the back surface of the mask was irradiated with ultraviolet rays at 10 J/cm² using a 193-nm ultraviolet lamp so that the light beam was applied to the pellicle agglutinant, as in Example 1.

After ultraviolet irradiation, the resultant was left for 1 hour at room temperature, and then the pellicle was slowly peeled upward from the mask substrate at a speed of 0.1 mm/sec.

When the mask substrate after peeling was visually observed, agglutinant residues were found in the entire portion to which the pellicle was bonded. The mass of the substrate after peeling was measured, and compared with the measured value before bonding. As a result, the mass difference was +3.50 mg.

EXPLANATION FOR REFERENCE NUMERALS

-   1: exposure original plate -   10: pellicle -   11: pellicle frame -   12: pellicle film -   13: adhesive material layer for bonding pellicle film -   14: agglutinant layer -   15: air pressure adjustment hole (vent) -   16: dust removal filter 

1. A pellicle comprising a pellicle film, a pellicle frame provided with the pellicle film on one end face thereof, and an agglutinant layer provided on the other end face of the pellicle frame, wherein when the agglutinant layer of the pellicle is bonded to a quartz mask substrate, then a portion to which the agglutinant layer of the pellicle is bonded is irradiated with 193-nm ultraviolet rays at 10 J/cm² from a back surface of the substrate, and the pellicle is peeled after the irradiation, an amount of peeling residues of the agglutinant layer remaining on the substrate is 0.5 mg or less.
 2. A pellicle as claimed in claim 1, wherein the agglutinant that forms the agglutinant layer comprises an acrylic polymer as a base material.
 3. A pellicle as claimed in claim 2, wherein the acrylic polymer comprises a (meth)acrylic acid ester having an ether bond as a monomer component.
 4. A pellicle as claimed in claim 3, wherein the (meth)acrylic acid ester having the ether bond is a (meth)acrylic acid ester having an alkylene oxide group.
 5. A pellicle as claimed in claim 4, wherein the alkylene oxide group is an ethylene oxide group.
 6. A pellicle as claimed in claim 2, wherein the acrylic polymer has a side chain containing an ether bond.
 7. A pellicle as claimed in claim 6, wherein the side chain containing the ether bond has an alkylene oxide group.
 8. A pellicle as claimed in claim 7, wherein the alkylene oxide group is an ethylene oxide group.
 9. A pellicle as claimed in claim 1, wherein the agglutinant that forms the agglutinant layer contains a polyvinyl ether compound.
 10. A pellicle as claimed in claim 1, wherein the agglutinant layer is irradiated with an exposure light beam.
 11. A pellicle as claimed in claim 1, wherein the pellicle is bonded to a phase shift photo mask.
 12. A pellicle as claimed in claim 1, wherein the pellicle is bonded to a negative type exposure original plate.
 13. A pellicle as claimed in claim 1, wherein the pellicle is bonded to an exposure original plate that has a non-shaded area or a semi-transparent shaded area in a portion thereof to which an agglutinant layer is bonded.
 14. A pellicle as claimed in claim 1, wherein the pellicle is bonded to an exposure original plate that has a transparent area in a portion thereof to which an agglutinant layer is bonded.
 15. A pellicle as claimed in claim 1, wherein the pellicle is bonded to a face comprising silicon oxide as a main component.
 16. A pellicle as claimed in claim 15, wherein the face comprising silicon oxide as a main component is a quartz face.
 17. A pellicle as claimed in claim 1, wherein the pellicle is compatible with regeneration cleaning with functional water.
 18. An exposure original plate with a pellicle, comprising an exposure original plate and a pellicle as claimed in claim 1 mounted on the exposure original plate.
 19. An exposure original plate with a pellicle as claimed in claim 18, wherein the exposure original plate is a phase shift photo mask.
 20. An exposure original plate with a pellicle as claimed in claim 18, wherein the exposure original plate is of negative type.
 21. An exposure original plate with a pellicle as claimed in claim 18, wherein a portion of the exposure original plate to which the agglutinant layer is bonded has a non-shaded area or a semi-transparent shaded area.
 22. An exposure original plate with a pellicle as claimed in claim 18, wherein a portion of the exposure original plate to which the agglutinant layer is bonded has a transparent area.
 23. An exposure original plate with a pellicle as claimed in claim 18, wherein the exposure original plate comprises silicon oxide as a main component.
 24. An exposure original plate with a pellicle as claimed in claim 18, wherein the exposure original plate is a quartz substrate.
 25. A method for producing a semiconductor device, comprising a step of performing exposure using an exposure original plate with a pellicle as claimed in claim
 18. 26. A method for producing a liquid crystal display board, comprising a step of performing exposure using an exposure original plate with a pellicle as claimed in claim
 18. 27. A method for regenerating an exposure original plate, comprising peeling a pellicle from an exposure original plate with a pellicle as claimed in claim 18, and cleaning residues of an agglutinant remaining on the exposure original plate with functional water to regenerate the exposure original plate.
 28. A peeling residue reduction method comprising, when peeling a pellicle from an exposure original plate to which the pellicle is bonded, reducing peeling residues of an agglutinant layer of the pellicle remaining on the exposure original plate, wherein the method uses a pellicle as claimed in claim 1 as the pellicle. 